JPH1121494A - Metallic luster oil-based ballpoint pen ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oil-based ink for a ball-point pen having a metallic luster, which is not so high in viscosity as to require a pressure unit.
Further, the present invention provides an oil-based ballpoint pen ink having a metallic luster color that does not cause clogging during storage and does not require a cap. SOLUTION: At least one organic solvent selected from the group consisting of alcohols and glycol ethers and N
-For a metallic lubricating oil-based ballpoint pen containing a vinyl acedamide polymerized crosslinked product and a metal flake pigment, and using an aluminum paste obtained by wetting an aluminum flake powder with at least one solvent selected from glycol ethers and glycols. Ink composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an oil-based ink composition for a ballpoint pen. More specifically, the present invention relates to an oil-based ballpoint pen ink composition having a metallic luster.

[0002]

2. Description of the Related Art Japanese Patent Application Laid-Open No. 60-186574 discloses an oil-based ink for a ballpoint pen having a metallic luster.
0000 cps or more), and a pressure unit such as a pressure ballpoint pen is required for use. JP-A-7-145339 discloses a water-based metallic luster ink for ballpoint pens containing aluminum powder, a natural polysaccharide, a water-soluble organic solvent and water and having a viscosity of 100 to 1,500 poise. JP-A-9-78021 discloses an oil-based ballpoint pen using a crosslinked N-vinylacetamide polymer.

However, Japanese Patent Application Laid-Open No. 60-186574
As described above, the publication requires a pressurizing unit for the outflow, which leads to an increase in cost.

The ink described in JP-A-7-145339 is a water-based ink technique. Aqueous ballpoint pens using that ink, like other aqueous ballpoint pens, require a so-called cap to seal the tip of the ballpoint pen tip.

Japanese Patent Application Laid-Open No. 9-78021 proposes an oil-based ballpoint pen to which an N-vinylacetamide-based monomer is added, and mainly uses a dye, carbon black or the like as a coloring agent to prevent ink from dripping. Explains the performance improvement. Although metal pigments such as aluminum powder are also arranged as usable colorants, they are not particularly aimed at metallic luster and there is no specific disclosure.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a writable print without the need for a complicated pressurizing unit, and to have a metallic luster color that does not cause clogging during storage and does not require a cap or the like. An object of the present invention is to provide an oil-based ballpoint pen ink.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that at least one organic solvent selected from the group consisting of alcohols and glycol ethers and N- It has been found that, in an ink containing a vinylacetamide polymerized crosslinked product, the purpose can be achieved by using a paste in which aluminum flaky powder is wetted with a specific solvent, and the present invention has been completed.

That is, the present invention relates to an ink containing at least one organic solvent selected from the group consisting of alcohols and glycol ethers and a crosslinked N-vinylacetamide polymer, wherein the ink is selected from glycol ethers and glycols. A metallic luster oil-based ballpoint pen ink composition using an aluminum paste obtained by prewetting aluminum flake powder with at least one solvent.

The organic solvent used in the composition of the present invention is at least one selected from the group consisting of alcohols and glycol ethers. Examples of the alcohols include high boiling alcohols such as benzyl alcohol and phenoxyethanol, and polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, and glycerin. Examples of glycol ethers include diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, and tripropylene glycol monomethyl ether. These solvents are for ensuring basic performance as a ballpoint pen ink, and are necessary not only for dissolving or dispersing the colorant, but also for obtaining appropriate drying properties of drawn lines. Particularly suitable main solvents include benzyl alcohol and 2-phenoxyethanol.

Aluminum is not commercially available as a powder as a coloring material as it is from the point of explosion-proof properties, and it is immersed in a liquid such as mineral spirits,
It is sold after surface treatment to prevent oxidation.
However, if the aluminum powder is used as it is, it tends to become a coagulated material called lumps at the time of dispersion. If the lumped material is used, a very small ink flow path such as a ballpoint pen tip tends to be clogged, and defects such as faint writing tend to occur. When a dispersion step (such as a ball mill) that involves a strong shear is used to eliminate the lump, aluminum may be discolored or lose its metallic luster. In addition, aluminum powder on the market as a coloring material is usually subjected to a surface treatment to prevent oxidation. However, in a dispersing process involving a too strong shear, a treated layer on the powder surface may fall off. There is also. Therefore, in the present invention, an aluminum paste in which the aluminum flaky powder is wetted in advance with a solvent such as glycol is used.

The aluminum paste used in the present invention is:
The aluminum powder is pre-wetted with at least one solvent selected from glycol ethers and glycols. The aluminum content in the aluminum paste is from 40 to 90% by weight. As the aluminum flaky powder, the product of the present invention is an oil-based ballpoint pen ink, but those which have been subjected to a rust-preventive treatment that can be used with a water-based ink are preferable, for example, phosphate esters, phosphates and phosphides, vanadates And those treated with chromium dimer acid, dimer acid, etc., and those encapsulated with an organic protective film (polymer) coat. Dispersion can be sufficiently dispersed by throwing into an ink vehicle and ordinary stirring.

As an aluminum paste wet-treated with glycol ether or glycol, for example, commercially available STAPA HYDOLAC P
M2, PM8, PM2n.l., PM8n.l., PM
16n.l., PM60n.l., PM65n.l., PM2
4n.l., BG2, BG8, BG2n.l, BG8
nl, BG16n.l, BG60n.l, BG65n.
l., BG24n.l., STAPA HYDOLAC P
M CHROMAL I, II, IV, VIII, X
(Eckart Co., Ltd.). The content of the aluminum paste in the ink is preferably 5 to 30% by weight in terms of powder. When the amount is less than 5% by weight, the metallic luster of the handwriting becomes poor, and when the amount exceeds 30% by weight, the quantitative discharge of the ink is adversely affected.

The thickener used in the ink of the present invention essentially contains an N-vinylacetamide polymerized cross-linked product.
A crosslinked product of vinylacetamide containing a nonionic acetamide group, for example, GX-205 (manufactured by Showa Denko KK). This product is considered to include the following structure.

Embedded image It is used as a ballpoint pen ink to prevent the sedimentation of the aluminum powder and to obtain a ballpoint pen tip and appropriate viscosity properties. If necessary, other general-purpose thickeners such as crosslinked acrylic acid and its modified products, silica, organically treated natural and synthetic viscosity minerals and the like can also be used in combination. The compounding amount is usually used in the range of 0.3 wt% to 5 wt%, and is set in accordance with the setting of the outflow amount, chips and the like.

Other colorants used in the ink composition of the present invention include dyes, organic, inorganic, and extender pigments that can be used in preparing a colored metallic glossy ink and are usually used in writing implements and paint inks. It is possible to use.
As the dye, any dye can be used as long as it is soluble in the above-mentioned solvents. Basic dyes, acid dyes, direct dyes and the like, as well as solubilized and microencapsulated dyes, may be used. For example,
Varifast Black # 1802, # 1805, #
3820, Varifast Violet # 1701, Varifast Yellow AUM, # 3104 (all manufactured by Orient Chemical Industries, Ltd.), Spiron Violet CR
H, Spiron Black CMHspecial, Spiron Yellow C-GNH, Spiron Orange GRH, Spiron Red BEH (all manufactured by Hodogaya Chemical Co., Ltd.), other auramines, rhodamines, methyl violet, malachite green, crystal violet, Victoria blue BOH And the like.

As the pigment, an inorganic pigment or an organic pigment may be used as it is, or a processed pigment or a dispersed toner whose surface has been modified with a resin or a surfactant may be used. For example, titanium oxide, carbon black, phthalocyanine, azo, anthraquinone, quinacridone, DPP (diketopyrrolopyrrole) microlease color (manufactured by Ciba Geigy), Fuji AS color (manufactured by Fuji Dye Co., Ltd.) And so on. These colorants are
They may be used alone or in combination of two or more. The amount of addition is not particularly limited, and may be an amount depending on the solubility or dispersing power of the colorant or an amount suitable for a desired hue or concentration, but is usually used in the range of 0.1 to 30% by weight. If the addition amount is too large, the metallic gloss color disappears and the writing performance deteriorates. If the addition amount is too small, there is no problem in the writing performance, but there is a drawback that the colored metallic gloss color deteriorates.

The ink composition of the present invention may contain, if necessary, an oil-based ink composition such as a resin, a preservative, a rust preventive, a defoamer, a lubricant, an anti-fog agent, a dispersant, and a surfactant. Conventional auxiliaries may be included. For example, as the resin, a resin commonly used in an ordinary oil-based ballpoint pen ink composition, for example, a ketone resin, a toluenesulfamide resin, a maleic acid resin, an ester gum, a xylene resin, an alkyd resin, a phenol resin, a terpene phenol resin, Rosin, polyvinylpyrrolidone, polyvinyl butyral, rosin alcohol, sucrose acetate isobutyrate and the like are used. These resins may be used alone or as a mixture of two or more, and the content thereof is in the range of 0.1 to 40% by weight based on the total amount of the ink composition. These resins have the effect of adjusting the viscosity of the ink composition or improving the fixability of the colorant, water resistance and dispersion stability, and when a liquid resin such as rosin alcohol and sucrose acetate isobutyrate is added, It is possible to reduce the amount of the organic solvent.

[0017]

Since the aluminum paste used for the oil-based ink for a ballpoint pen having a metallic luster color is wetted in advance with at least aluminum powder and a glycol ether or glycol, an organic solvent in which the glycol ether or glycol is a main solvent, for example, benzyl Alcohol, 2
-Dispersion is good due to good compatibility with phenoxyethanol and the like, and particularly, a large apparently considered to be considered that the crosslinked N-vinylacetamide polymer swells and disperses in the ink composition to form a gel, and the action gives thixotropy. It is presumed that since the aluminum pigment is uniformly dispersed and maintained in the solution having the viscosity, the amount of the ball-point pen flowing out from the pen tip is good and clogging and blurring can be prevented. In addition, the large apparent viscosity allows the ink to be directly stored in the small-diameter ink storage tube, and the rotation of the ball during writing increases the shear rate near the ball, decreases the apparent viscosity, and increases the fluidity at the pen tip. Therefore, a writing implement can be constituted by a so-called ordinary tip and a small-diameter ink storage tube without using an expensive pressurizing unit.

[0018]

Next, the present invention will be described in more detail by way of examples. The present invention is not limited by this embodiment. (Parts) in Examples and Comparative Examples indicates parts by weight. The ink compositions obtained in the examples and comparative examples were filled in ink storage tubes made of polypropylene tubes having an inner diameter of 2 mm. The following test was performed using a ballpoint pen equipped with this ink storage tube and a stainless steel tip.

(A) Writing test: The sample was left in a constant temperature / humidity bath at 25 ° C. and 65% RH for 1 day, and a handwritten spiral writing having a diameter of about 4 cm was performed to observe the drawing state. Those that did not cause ink leakage were evaluated as ○, and those that caused ink were evaluated as ×.

(B) Ink leak test: 25 ° C., 65% R
The pen tip was left for 3 days in a constant temperature and humidity chamber, and the presence or absence of ink leakage was checked.

(C) Storage test: Left in a 40 ° C. constant temperature bath for 4 weeks, and then left in a 25 ° C., 65% RH constant temperature / humidity bath for 1 day to write a handwritten spiral writing about 4 cm in diameter. The drawn line condition was observed. The handwriting was evaluated sensually.

(Example 1) Aluminum paste 15 parts (STAPA HYDROLAC PM Chromal VIII: manufactured by ECKART Co., Ltd .; aluminum powder content: about 70%, including propylene glycol monomethyl ether as a solvent) Rosin alcohol 10 parts Benzyl alcohol 15 .4 parts 2-phenoxyethanol 59 parts polyvinylpyrrolidone K90 0.4 parts N-vinylacetamide crosslinked polymer: GX-205: 0.6 parts (manufactured by Showa Denko KK)

(Example 2) (Red metallic ink) Aluminum paste 8 parts (STAPA HYDROLAC BG8n.l., manufactured by ECKART Co .; aluminum powder content 65%, butyl glycol as other solvent) Red pigment Paste 20 parts (Pigment, mixture of polyvinyl butyral resin containing 15% of CI Pigment Red 17 and benzyl alcohol) Rosin alcohol 20 parts Benzyl alcohol 20 parts 2-phenoxyethanol 31.3 parts Polyvinylpyrrolidone K90 0.3 part N-vinylacetamide polymerization cross-linking Product: GX-205: 0.4 part (manufactured by Showa Denko KK)

(Comparative Example 1) About 70% of aluminum powder and about 3 of mineral spirit
Ink replaced with 0% Toyo Aluminum 0240M.

Comparative Example 2 About 64% of aluminum powder and about 3 of mineral spirits were prepared by using the aluminum paste of Example 2
Ink replaced with 6% Toyo Aluminum 1200M.

Comparative Example 3 The whole amount of the crosslinked N-vinylacetamide polymer of Example 1 was replaced with a ketone resin.

(Evaluation Criteria) Evaluation in the turning writing test ○: Good without blurring Δ: Partially blurred but recovered immediately. ×: Blurring continued for 10 or more turns. DC: No ink leakage occurred. ×: Ink leakage occurred

[0028]

[Table 1]

As is clear from Table 1, in Examples 1 and 2, the aluminum pigment was uniformly dispersed, and it was possible to write without blurring in the writing test. The initial state was maintained after the storage test. On the other hand, in the case where the mineral solvent, which is a petroleum-based solvent, was used as the wetting solvent for the aluminum powder pigment, it took a long time to disperse the aluminum powder, and in the storage test, a gel-like precipitate was generated in the ink.

[0030]

The present invention does not require a complicated pressurizing unit,
An oil-based ink for a ball-point pen that can be written, has no clogging during storage, and has a metallic luster that does not require a cap for preventing evaporation is provided.

Claims (3)

[Claims] An organic solvent selected from the group consisting of alcohols and glycol ethers and at least one organic solvent
-In an oil-based ink for a ball-point pen containing at least a vinylacetamide polymerized crosslinked product and a metal flake pigment, as the metal flake pigment, aluminum obtained by wetting aluminum flake powder with at least one solvent selected from glycol ethers and glycols An ink composition for a metallic luster oil-based ballpoint pen using a paste. 2. The oil-based ballpoint pen ink composition having a metallic luster color according to claim 1, wherein the glycol ether organic solvent which wets the aluminum flake pigment is propylene glycol monomethyl ether. 3. The oil-based ballpoint pen ink composition having a metallic luster color according to claim 1, wherein the glycol obtained by wetting the aluminum flake powder is butyl glycol or propylene glycol.